Cellulose organic ester composition containing an ether of diethylene glycol monoacetate



Patented July 23, 1935 CELLULOSE ORGANIC ESTER COMPO ITI N ONTA NING AN ETHE F DIETHY E GLYCOL MONOACETATE Stewart J. Carroll, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New York No Drawing. Application 'July 29, 1932, Serial No. 626,232

4 Claims. (Cl. 10640) I This invention relates to compositions of matter in which cellulose organic esters, such as cellulose acetate, are combined or mixed with other substances, such as a compatible plasticizer, with or without a common solvent for both, and with or without other useful addition agents, so that the resulting product will have properties such as will make the composition highly advantageous 'for use in the plastic and analogous arts, such, for instance, as the manufacture of wraping sheets or tissue, photographic film, molding compounds and products, artificial silk, varnishes or lacquers, coating compositions and the like.

Qne object of this invention is to produce com.- positions of matter which may be made into permanently transparent, strong and flexible sheets or films of desired thinness which are substantially waterproof, are unaffected by ordinary photo raphic fluids and possess the desired properties of a support for sensitive photographic coatings. Another object of my invention is to produce compositions of matter which are capable of easy and convenient manipulation in the plastic and analogous arts, such as in the manuiacture of sheets, films, artificial silk filaments, varnishes,

lacquers and the like, and to produce compositions which will not injure, or be injured by, the "substances or surfaces with which they are asso- ,ciated during manufacture. Another object of my invention is to. produce compositions which can be molded at elevated temperatures and high pressures to produce plastic products having the desirable properties of celluloid. Still another object of my invention is to produce compositions of matter containing cellulose acetate which have a high degree of flexibility, softness and pliability. Other objects will become apparent to those skilled in the art to which thisinvention pertains. While cellulose acetate has been known for decades, it has also been known that to utilize it in the various plastic arts it is necessary to therewith such plasticizing or conditioning agents as trinhenyl phospha m a ht a en or the like. Certain of these and other addition agents are also added for the purpose of reducing the infiainmabilityof the PI'Oduct. Plastic inducing, agents, such as the higher alcohols and their ester-Stare sometimes also added. Similarly, addition compounds of various kinds have been employed to increase flexibility, transparency, toughness and other properties which will enhance the value of the resulting product. Addition products for the same or similar purposes are also added to cellulose acetate to prepare it for use in the other plastic arts, suc as in t ma ufac ure o a qu rs, varn he ar fi al lk filaments. m l d com unds and he ke Whfl be Plasticizers or other addition agents heretofore discov ed a had t e r ut ty n theart the nc easin u o wh ch cellu ose ce ate been 5 pu an the n eas n numb o desirable were er r qui d of e u ose a et te for most 91,1 p e e mad th di cove y o and seeemi a la z rs o ot er eu iiien agent a ma er of n de ab mpe tane to he rthis a be a o l o em d ieulty, sinu man f he n ro l ul e o v nt re no @01- ni for cellulose a a e, and man sub ances wh h a a la ti z f r i cellule e re e ufi e nt c m tib wi h eel es ace ate to be us d a plasticizers in ce u o ace at eem qsitions. 4

I a e dis o e tha a ua e p r es ma b indu ed in and/o c t bute t o it ons containing organic esters of cellulose, such as cellu o ia tate, by ad n ther t a a le tieizine co po nd an t r e d eth en gl l m neeeea e s h. r nsta as h th l b t l, e benz l ether o me hy en l o mon a tete- The pa i u y us fu ropert es h c thes co po nds. induce i or c n ibut in ee ulosi com o i ns Containing t em are h nafter r muner e The e s o die ne l c m ne ee et may be pa a iel ewshe m ne t ier oi siiethy ne sly e whose a a it i desired to pr pare i placed in a r nd-b tom d la e uine-ed th a tir r, d o p n funn l and reflux l ane s an h a d 1. a steam ba h o e m era.- ur of 40 or 5 C, a ex e oi e c nhydride say om 1 5 to 5 mole f a e anh driue ier each mo o methy e e sire-Q1 m nee h r is a d in po io r u h th dro p ng unnel, with s irr n Aft t addi ion of the a eiie ydrid s omp ete, th rea ion mix ur i refluxed. with tir i for o e t We h u s- The ac t c aci form d, tee-e he withu eli eei [a eti anhydriee i th n di i led f t t-atmospheri Pressur In t e eas 9 the hyl 9 e of d eth l n l o me e ete wh ch be is a 20 0 .0 the uc m y 't en'b "di tille ov at atmo ph pres ure In the e e o pr u t o hi h r m leeularw isht su h as. the buty an ben eth s i ,uie hvl ue g ycel'menoacetate, the product should be distilled g inder d m ni he r sur h bu y ether of ieinylene glycol monoacetate boils at 119-120 ,C. atB

m n. pressure. The benzyl ether Qf diethylene glyc l me eaeetat boi a ii -8 1 a 8 mm- Pre r v 1 In order that those skilled in this art may better understand my invention I would state, by way of illustration, that for the manufacture of photographic film or other sheets my new compositions of matter may be compounded as follows: 100 parts of acetone-soluble cellulose acetate, i. e. cellulose acetate containing from 36% to 42% acetyl radical, approximately, is dissolved with stirring at atmospheric temperature in 300 to 500 parts, preferably 400 parts, by weight, of acetone. To this solution may be added from 10 to 50 parts by weight of an ether of diethylene glycol monoacetate, such as the ethyl, butyl, or benzyl ether of diethylene glycol monoacetate. Within the limits stated, the amount of plasticizer may be decreased or increased, depending upon whether it is desired to decrease or increase, respectively, the properties which these plasticizers contribute to the finished product. The amount of solvent employed may also be increased or decreased, depending upon whether it is desired to have a more or less freely flowing composition, respectively.

A composition of matter prepared as above described may be deposited upon any suitable filmforming surface to form a film or sheet, in a manner well known to those skilled in the art. sheet so produced has permanently brilliant transparency (even where as much as 50 to 60 parts of the plasticizer per 100 parts of cellulose organic ester, such as cellulose acetate, is used) and low inflammability, burning no more readily than ordinary newsprint. Films or sheets produced in accordance with my invention are tough and flexible. For instance, sheets of cellulose ace tate plasticized with from 20% to 50% (parts by weight based on the cellulose acetate) of the ethyl ether of diethylene glycol monoacetate had an initial flexibility of from 65% to 200% greater than that of sheets containing no plasticizer. Sheets containing from 10 to 50% of the butyl ether of diethylene glycol monoacetate had an initial flexibility of from 100% to 500% greater than that of sheets containing no plasticizer. Sheets containing from 20 to 50% of the benzyl .ether of diethylene glycol monoacetate had an initial flexibility of from 135% to 500% greater than that of sheets containing no plasticizer. Furthermore, a sheet so plasticized maintains flexibility in a superior fashion. For instance, sheets containing from 10 to 50% of the butyl ether of diethylene glycol monoacetate maintained flexibility at 65 C. for 114 days, whereas an unplasticized film became brittle in 30 days. This indicates that films so plasticized will withstand ordinary usage satisfactorily for many years.

Other similar solvents (instead of acetone) which are compatible with the cellulose acetate and my new plasticizers will also occur to those skilled in this art, such as ethylene chloride-alcohol mixtures. In like manner these plasticizers may be compounded with other single organic esters of cellulose, such as cellulose propionate,

butyrate, stearate and the like, or with mixed organic esters, such as cellulose aceto-stearate,

cellulose aceto-propionate, cellulose aceto-butyrate, cellulose aceto-lactate, cellulose aceto-tartrate or the like, a suitable solvent which will dissolve both the cellulosic derivative and the plasticizer being employed, such, for instance, as an alkylene chloride with or without the addition of alcohol.

Inasmuch as my above-described compositions of matter are useful in the production of films and sheets, it will be apparent that my new plasticizers may also be employed with advantage in the other branches of the plastic art. For instance, my above-described compositions of matter may be employed in the manufacture of artificial silk by the dry spinning method. With the proper coagulating bath they may also be employed for wet spinning. My novel plasticizers may also be employed with advantage in connection with a number of the known lacquer and varnish formulae with which they may be found to be compatible. In such cases the plasticizer is usually first put into solution in the cellulose derivative solution, and if non-solvents are added for the purpose of cheapening the composition they are added only to such an extent as will not precipitate the derivative from solution. Also the plasticizer is usually employed in rather large amounts, such as from 50 to 60 parts, in compounding lacquers. Other uses within the scope of my invention will also suggest themselves to those skilled in the art and are to be included within the scope of the claims appended hereto.

The ethers of diethylene glycol monoacetate may also be advantageously used as plasticizers in cellulose acetate molding compositions. For instance when about 30% (parts by weight based on the cellulose acetate) of the butyl or ethyl ether of diethylene glycol monoacetate is homogeneously mixed with cellulose acetate, the mixture may be converted into a hard, transparent plastic product by molding at a temperature of 140-160" C. and a pressure of from 2500 to 4000 pounds per square inch for a period of from 2 to 5 minutes, in a manner already known to those skilled in molding compounds of that nature.

Moreover, I have found that, upon the addition to cellulose acetate of approximately 100% of the ethyl, butyl, or benzyl ether of diethylene glycol monoacetate, quite unexpected compatibility of the plasticizer with the cellulose acetate exists and also that quite unexpected flexibility, plasticity and clarity of the final product results. Contrary to experience in most cases where such a large proportion of plasticizer is used, no exudation or crystallizing out of the plasticizer occurs. Compositions containing approximately 100% of an ether of diethylene glycol monoacetate have great utility where ahighly flexible compound is desired, such as in the coating of a base (for instance, cloth or other fabric) in the production of artificial leather, or in the production of relatively thin sheets wherein more than the usual flexibility is important. Such a composition, if converted, for instance, into sheet form will be found to be supple and non-rigid, and to have the ability to conform readily to a surface upon which it'may be placed, and this even at atmospheric temperatures.

These novel compositions of matter are produced by merely mixing the plasticizer with cellulose acetate and then adding sufficient of a common solvent, such as acetone, whereupon an intimate mixture of the plasticizer with the cellulose acetate results. The amount of acetone or other common solvent to be employed varies, of course, within rather wide limits depending upon the fluidity of the composition desired. 100 parts of acetone will sufiice for many purposes, although I prefer to use 400 parts. Various high boilers or evaporation retardents, such as ethyl lactate, amyl acetate or the like may also be added if desired, as is well known in this art.

The compositions of matter so produced may then be coated into sheets in the usualway by depositing them upon plates or rolls and permitting the solvent to evaporate. If my novel compositions are to be employed in the manufacture of artificial leather, they may be coated upon, for instance, a cloth support and the solvent permitted to evaporate, or the cloth support may be caused to pass through the cellulose acetate-plasticizer composition and permitted to absorb the solution, the solvent in the coating being then permitted'to evaporate. In either case, the solvent may, of course, be recovered if desired by condensing the vapors, etc.

While above andin certain of the claims appended hereto, I have referred to the use of a plasticizer in approximately equal proportions, namely in a ratio of approximately 100%, it will be understood that within this terminology variations of from 10% to 15% less than 100% of plasticizer and as much as to more than of the plasticizer may in some instances be desirable.

What I claim as my invention and desire to be secured by Letters Patent of the United States is:

1. A composition of matter comprising cellulose acetate and the butyl ether of diethylene glycol monoacetate.

2. A flexible, transparent sheet comprising 100 parts of cellulose acetate and. about 10 to 50 parts, by weight, of the butyl ether of diethylene glycol monoacetate.

3. A molding composition adapted for molding under elevated temperatures and high pressures, comprising cellulose acetate and the butyl ether of diethylene glycol monoacetate.

4. A molded object comprising cellulose acetate and the butyl ether of diethylene glycol monoacetate.

STEWART J. CARROLL. 

